TWI608032B - Fiber and method of manufacturing the same - Google Patents

Description

Fiber and its manufacturing method

The present disclosure relates to fibers, and more particularly to their polyester composition.

Polyethylene terephthalate has excellent properties and wide application, and is the basic raw material of many industrial products. However, the raw materials of polyethylene terephthalate depend on petroleum resources, and biomass-plastic is considered as a good choice to replace polyethylene terephthalate. More and more research resources are put into raw materials. Development of plastics. The precious petrochemical resources that are gradually depleted can be reserved for more valuable use in later generations.

However, there is still a need to improve the properties of raw materials in the processing of raw plastics. At present, there is a need for raw plastics with excellent processability and mechanical properties, and they are applied to fibers.

The fiber provided by an embodiment is obtained by copolymerizing a diacid, a diacid ester, or a combination thereof with a polyhydric alcohol, wherein the diacid, the diacid ester, or the combination thereof comprises (1) furan. a dicarboxylic acid, a furan dicarboxylate, or a combination thereof, or (2) a furan dicarboxylic acid, a furan dicarboxylate, or a combination thereof, and a spirobiic acid, and the polyol comprises (3) C ₂ -C _a polyol of ₁₄ or (4) a C ₂ -C ₁₄ polyol and a spiro diol, wherein the spiro diol has the structure of formula (I): , wherein the spirobiic acid has the structure of formula (II): , wherein each R ^{2 is} independently a single bond, , , Or a C ₁ -C ₄ linear alkylene group, each R ^{3 is} independently , or . The diacid, the diacid ester, or a combination thereof, is compatible with the polyol: (a) the diacid, the diacid ester, or a combination thereof comprising (2) furan dicarboxylic acid, furan diformate, or The combination of the above and the spirobiic acid, (b) the polyol comprises (4) a C ₂ -C ₁₄ polyol and a spiro diol, or (c) a combination thereof. The polyester has an intrinsic viscosity at 30 ° C of between 0.5 dL/g and 1.5 dL/g.

The method for producing a fiber according to an embodiment of the present invention comprises: mixing a diacid, a diacid ester, or a combination thereof, and a polyol to carry out an esterification reaction and a polycondensation reaction to form a prepolymer, and prepolymerizing the prepolymer. Solid state polymerization to form a polyester; and spinning polyester to form fibers. The diacid, the diacid ester, or a combination thereof comprises (1) furan dicarboxylic acid, furan dicarboxylate, or a combination thereof, or (2) furan dicarboxylic acid, furan dicarboxylate, or the like Combining with a spirobiic acid, and the polyol comprises (3) a C ₂ -C ₁₄ polyol or (4) a C ₂ -C ₁₄ polyol and a spiro diol, wherein the spiro diol has the formula (I) Structure: , wherein the spirobiic acid has the structure of formula (II): Each of R ^{2 is} independently a single bond, , , Or a linear alkylene group of C ₁ -C ₄ , each R ^{3 is} independently , or And the diacid, the ester of the diacid, or a combination thereof, is compatible with the polyol: (a) an ester of a diacid or a diacid, or a combination thereof comprising (2) furan dicarboxylic acid, furan The acid ester compound, or a combination thereof, and the spirobiic acid, (b) the polyol comprises (4) a C ₂ -C ₁₄ polyol and a spiro diol, or (c) a combination thereof. The inherent viscosity of the polyester at 30 ° C is between 0.5 dL / g and 1.5 dL / g.

In one embodiment of the invention, the polyester is formed by copolymerization of a diacid, a diacid ester, or a combination thereof with a polyol. In an embodiment of the present disclosure, a diacid, a diacid ester, or a combination thereof is mixed with a polyol to carry out an esterification reaction and a polycondensation reaction to form a prepolymer, and then the solid polymer is polymerized on the prepolymer. To form a polyester.

In one embodiment of the present disclosure, the diacid, the diacid ester, or a combination thereof comprises (1) furan dicarboxylic acid, furan dicarboxylate, or a combination thereof, or (2) furan dicarboxylic acid, furan An acid ester, or a combination thereof, and a spirobiic acid.

In one embodiment of the present disclosure, the furan dicarboxylic acid may comprise 2,5-furandicarboxylic acid, 3,4-furandicarboxylic acid, 2,3-furandicarboxylic acid or a combination thereof. The furan diformate may comprise dimethyl 2,5-furandicarboxylate, dimethyl 3,4-furandicarboxylate, dimethyl 2,3-furodicarboxylate or a combination thereof. Spirobiic acid has the structure of formula (II): , wherein each R ^{2 can} independently be a single bond, , , Or a C ₁ -C ₄ linear alkylene group, each R ³ independently being , or .

In one embodiment of the present disclosure, the polyol comprises (3) a C ₂ -C ₁₄ polyol or (4) a C ₂ -C ₁₄ polyol and a spiro diol.

In one embodiment of the present disclosure, the polyol may comprise a C ₂ -C ₈ polyol such as a C ₂ -C ₆ linear diol. In an embodiment of the present disclosure, the polyol may comprise ethylene glycol, 1,3-propanediol, glycerol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6- Hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, decanediol, undecanediol, dodecanediol, tetradecanediol, Rosin diol, isosorbide, 2,5-furan diol or a combination thereof. The spiro diol has the structure of formula (I): Each R ^{2 can} independently be a single bond, , , Or a C ₁ -C ₄ linear alkylene group, each R ³ independently being , or .

In one embodiment of the present disclosure, the diacid, the diacid ester, or a combination of the above and a monomer such as a polyol are selected according to the following conditions (a), (b), or (c): (a) a diacid, The diacid ester, or a combination thereof, comprises (2) furan dicarboxylic acid, furan dicarboxylate, or a combination thereof and spirobiic acid; (b) the polyol comprises (4) C ₂ -C ₁₄ a polyol and a spiro diol; or (c) a combination of the above.

In an embodiment of the present disclosure, the esterification reaction comprises a transesterification reaction or a direct esterification reaction, and both the esterification reaction and the polycondensation reaction can be catalyzed by a suitable catalyst, and the catalyst content is about 25 to 500 ppm of the reactant. In one embodiment of the present disclosure, the catalyst may be a tin catalyst, a lanthanide, a gallium, an aluminum, a titanium, a lanthanide, a lithium, a magnesium, a manganese, a cobalt, or a combination thereof. For example, the catalyst can be a titanium based solid catalyst, titanium isopropoxide, titanium isobutoxide, or a combination thereof. The reaction temperature of the esterification reaction and the polycondensation reaction is respectively between 170 ° C and 260 ° C, and the reaction time is respectively between about 1 hour and 8 hours.

After the esterification reaction and the polycondensation reaction form a prepolymer, the prepolymer is subjected to solid state polymerization, and the reaction temperature of the solid state polymerization reaction is between 170 ° C and 210 ° C, and the reaction time is about 4 hours to 120 hours. Between or between 16 hours and 56 hours. If the solid state polymerization temperature is too high or the reaction time is too long, yellowing and melting and agglomeration tend to occur during the process. If the solid state polymerization temperature is too low or the reaction time is too short, it is difficult to achieve the purpose of increasing the molecular weight.

In an embodiment of the present invention, before the solid polymerization of the prepolymer, the recrystallization step may be further included, and the temperature of the recrystallization step is between about 110 ° C and 170 ° C (for example, between about 130 ° C and 160 ° C). Between), the time of the recrystallization step is between about 0.5 hours and 2 hours. Thereafter, the solid obtained by the recrystallization step is pulverized, and the obtained powder is subjected to solid state polymerization.

In an embodiment of the present disclosure, during the solid state polymerization reaction, the spirobiic acid or the spirocyclic diol undergoes a ring opening reaction, the prepolymer is branched, the molecular weight is increased, and the zero shear viscosity is increased. Obtaining a polyester; if R ² is , R ³ is As an example, a schematic diagram of a solid state polymerization reaction is as follows: P' is the other part of the polyester.

In an embodiment of the present invention, the spirocyclic diacid or spiro diol monomer can be used to make the solid polymerized polyester have good zero shear viscosity, which can be beneficial to the forming process of various articles (such as containers). In some applications, the problem of parison sagging of the polyester during the forming process can be improved.

In one embodiment of the present disclosure, the diacid, the diacid ester, or a combination thereof comprises 1 mole of (1) furan dicarboxylic acid, furan dicarboxylate, or a combination thereof, and the polyol comprises 1 to 3 moles of (4) C ₂ -C ₁₄ polyol and spiro diol. The molar ratio of furan dicarboxylic acid, furan dicarboxylate, or a combination thereof, to the spirocyclic diol is between about 1:0.0003023 and 1:0.0012092. If the amount of the spiro diol is too large, gelation tends to occur, which is disadvantageous for processing applications. If the spiro diol is too small, it is difficult to achieve the effect of increasing the zero shear viscosity.

In one embodiment of the present disclosure, the diacid, the diacid ester, or a combination thereof comprises 1 mole of (2) furan dicarboxylic acid, furan diformate, or a combination thereof and spirobiic acid, The polyol comprises from 1 to 3 mole parts of (3) C ₂ -C ₁₄ polyol. Wherein the furan dicarboxylic acid, the furan diformate, or a combination of the above and the spirobiic acid has a molar ratio of between about 99.998: 0.002 to 99.9999: 0.0001 or between about 99.9985: 0.0015 to 99.9999: 0.0001. . If the spirobiic acid is too much, gelation tends to occur, which is disadvantageous for processing applications. If the spirobiic acid is too small, it is difficult to achieve the effect of increasing the zero shear viscosity.

In one embodiment, the polyester may be further blended with other polyesters as desired to form a blend. In one embodiment, the polyester may be further mixed with other additives such as antioxidants, leveling agents, pigments, or the like, depending on the needs.

The above polyester can be used as a fiber, and the inherent viscosity of the polyester at 30 ° C is between about 0.5 dL / g and 1.5 dL / g. If the inherent viscosity of the polyester is too high, the fluidity may be poor, and the melt spinning is required at a higher temperature, and the polyester is liable to be degraded. If the inherent viscosity of the polyester is too low, the molecular weight may be too low and the mechanical properties may be poor. In one embodiment, the polyester may be spun to form fibers, and the spinning process may be a melt spinning process, a dry spray wet spinning process, an emulsion or suspension spinning process, a film split spinning process, or other suitable process. In one embodiment, the collection rate of the collection fibers can be between 100 meters/minute and 3000 meters/minute, or between 300 meters/minute and 1500 meters/minute. If the winding rate is too high, it may be prone to breakage. If the winding rate is too low, the degree of elongation may be insufficient, the degree of crystallization may be low, and the mechanical strength may be weak. The above fibers may be used as they are, if the fibers are further extended at a temperature of from 60 ° C to 150 ° C. The length of the expanded fiber is between 1.1 and 5 times the length of the fiber before stretching. The above additional extension step can further improve the elongation at break and crystallinity of the fiber. In one embodiment, the fibers have an elongation at break of between 5% and 250%, or between 14% and 210%. If the elongation at break is too low, the fiber is easily broken. In an embodiment, the fiber The crystallinity is between 5 J/g and 60 J/g. If the crystallinity of the fiber is too high, the fiber may be broken and the fiber is inelastic, and the fiber is difficult to dye. If the crystallinity of the fiber is too low, the fiber strength may be insufficient.

The above and other objects, features and advantages of the present invention will become more apparent and understood.

Example

Example 1

1 mole of dimethyl 2,5-furandicarboxylate, 2.5 moles of ethylene glycol, 500 ppm of 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2 , 4,8,10-tetraoxaspiro[5.5]undecane (hereinafter referred to as SPG monomer), and the weight of the SPG monomer relative to the dimethyl 2,5-furandicarboxylate is about 500 ppm (ie 0.03023 mol) %), with 100ppm (relative to the weight of dimethyl 2,5-furandicarboxylate) of titanium-based solid catalyst (purchased from Dingxing Industrial Co., Ltd. C-94), placed in the reaction tank, with condensation Device and methanol collection cylinder. Nitrogen gas was introduced, and the salt bath temperature was set to 190 ° C, and the stirrer rotation speed was 200 rpm to carry out the transesterification reaction. When the catalyst is completely dissolved, methanol is condensed in the condenser. After three hours of reaction, the condensed methanol is removed and 0.1% by weight (relative to the weight of dimethyl 2,5-furandicarboxylate) of the antioxidant is added ( From Irganox 1010) from BASF, the pressure in the reaction system was gradually reduced to 50 torr in 30 minutes to remove excess ethylene glycol. The salt bath temperature was gradually increased to 230 ° C and the reaction pressure was gradually lowered to below 1 torr, and the reaction was continued for 60 minutes to carry out a polycondensation reaction. Finally, the vacuum was broken with nitrogen and the heating and stirring were stopped, the reaction tank lid was taken apart, and the viscous product was taken out.

The above product was recrystallized at 150 ° C for one hour, then pulverized by a pulverizer and separated by a sieve, and a powder of less than 25 mesh was taken for solid state polymerization. Take the above powder in the reaction tank and set the salt bath temperature to 200°. C was subjected to a solid polymerization reaction, the reaction pressure was lower than 1 torr, and after 48 hours of reaction, a branched polyester was obtained, and the branched polyester was taken out for characteristic analysis, and the intrinsic viscosity (at 30 ° C) and rheological properties are shown in Table 1.

Embodiment 2 and Embodiment 3

The same procedure as in Example 1 was carried out, in which the amount of SPG monomer used and the properties of the product are listed in Table 1.

Comparative example 1

The same procedure as described in Example 1 was carried out in which no SPG monomer was used. The properties of the product are listed in Table 1.

Comparative example 2

Same as the method described in Example 1, in which no SPG monomer was used, and another 1000 ppm (relative to the weight of dimethyl 2,5-furandicarboxylate) having a spiro ring structure (Irgafos 126 available from BASF, structure) was added. for ). The properties of the product are listed in Table 1.

Comparative example 3

Same as the method described in Example 1, wherein no SPG monomer was used, and another 1000 ppm (relative to the weight of dimethyl 2,5-furandicarboxylate) compound having an aromatic ring (Irgafos 168 available from BASF) was used. ). The properties of the product are listed in Table 1.

It can be seen from the first table that the zero shear viscosity of the products of Examples 1 to 3 is greatly improved compared with Comparative Example 1, and it is known that the addition of SPG monomer can greatly improve the zero shear viscosity of the polyester after solid state polymerization to achieve good Processability. Moreover, regardless of whether or not the SPG monomer is added, the intrinsic viscosity of the product rises due to solid state polymerization. However, only the embodiment in which the SPG monomer is added can achieve a good zero shear viscosity, even if the compound having a spiro structure is added in Comparative Example 2. (Non-spirocyclic diol) also does not achieve good zero shear viscosity.

Example 4

1 mole of dimethyl 2,5-furandicarboxylate, 2.5 moles of ethylene glycol, 1500 ppm (relative to the weight of dimethyl 2,5-furandicarboxylate, about 0.09069 mol%) of SPG A titanium solid catalyst (acquired from C-94 of Dingxing Industrial Co., Ltd.) with 100 ppm (relative to the weight of dimethyl 2,5-furandicarboxylate), placed in a reaction tank, and equipped with a condensing device Collect the cylinder with methanol. Nitrogen gas was introduced, and the salt bath temperature was set to 190 ° C, and the stirrer rotation speed was 200 rpm to carry out the transesterification reaction. When the catalyst is completely dissolved, methanol is condensed in the condenser. After three hours of reaction, the condensed methanol is removed and 0.1% by weight (relative to the weight of dimethyl 2,5-furandicarboxylate) of the antioxidant is added ( From Irvineox 1010) from BASF, gradually put the pressure inside the reaction system at 30 Reduce to 50 torr in minutes to remove excess ethylene glycol. The salt bath temperature was gradually increased to 230 ° C and the reaction pressure was gradually lowered to below 1 torr, and the reaction was continued for 60 minutes to carry out a polycondensation reaction. Finally, the vacuum was broken with nitrogen and the heating and stirring were stopped, the reaction tank lid was taken apart, and the viscous product was taken out.

The above product was recrystallized at 150 ° C for one hour, then pulverized by a pulverizer and separated by a sieve, and a powder of less than 25 mesh was taken for solid state polymerization. Six grams of powder was placed in the reaction tank, and the salt bath temperature was set to 200 ° C for solidification reaction. The reaction pressure was lower than 1 torr. After 24 hours of reaction, the product was taken for characteristic analysis. The viscosity and rheological properties are listed in Table 2.

Example 5

The same procedure as described in Example 4, in which the amount of SPG monomer used and the properties of the product are listed in Table 2.

Comparative example 4

The same procedure as in Comparative Example 1, in which the solidification reaction was changed to 24 hours. The properties of the product are listed in Table 2.

As can be seen from the second table, the zero shear viscosity of the products of Examples 4 to 5 and comparison Compared with the case of Example 4, it is known that the addition of SPG monomer can greatly improve the zero shear viscosity of the polyester after solid state polymerization to achieve good processability.

Comparative Example 5

The procedure was the same as in Example 2 except that the time of the solid state polymerization was changed to 24 hours, and the SPG monomer was changed to pentaerythritol (PENTA). The properties of the product are listed in Table 3.

As is clear from the third table, in Comparative Example 5, the use of pentaerythritol in place of the SPG monomer causes gelation. The embodiment of the present disclosure can be added to a reaction vessel by using a SPG monomer together with a diacid, a diacid ester, or a combination thereof in combination with a monomer such as a polyol, without gelation. Good zero shear viscosity polyester.

Example 6

1 mole of furan-2,5-dicarboxylic acid dimethyl ester, 2.5 moles of 1,3-propanediol, 1000 ppm of SPG monomer (relative to dimethyl furan-2,5-dicarboxylate of about 0.06046) Mol%) and 200ppm (relative to the weight of dimethyl 2,5-furandicarboxylate) of titanium-based solid catalyst (purchased from Dingxing Industrial Co., Ltd. C-94), placed in the reaction tank, with condensation Device and methanol collection cylinder. Pass nitrogen gas and set the salt bath temperature to 190 °C. The transesterification reaction was carried out at a stirrer speed of 200 rpm. When the catalyst is completely dissolved, methanol is condensed in the condenser. After three hours of reaction, the condensed methanol is removed and 0.1% by weight (relative to the weight of dimethyl 2,5-furandicarboxylate) of the antioxidant is added ( From Irganox 1010) from BASF, the pressure in the reaction system was gradually reduced to 50 torr to remove excess propylene glycol in 30 minutes. The salt bath temperature was gradually increased to 230 ° C and the reaction pressure was gradually lowered to below 1 torr, and the reaction was continued for 180 minutes to carry out a polycondensation reaction. Finally, the vacuum was broken with nitrogen and the heating and stirring were stopped, the reaction tank lid was taken apart, and the viscous product was taken out.

The above product was recrystallized at 120 ° C for one hour, then pulverized by a pulverizer and separated by a sieve, and a powder of less than 25 mesh was taken for solid state polymerization. Six grams of powder was placed in the reaction tank, and the solidification reaction temperature was set to 160 ° C for solidification reaction. The reaction pressure was lower than 1 torr. After 48 hours of reaction, the product was taken for characteristic analysis. Viscosity and rheological properties are listed in Table 3.

Comparative Example 6

The same procedure as described in Example 6, except that no SPG monomer was added. The characteristics of the product are listed in Table 4.

As can be seen from the fourth table, the sample of Example 6 is zero compared to the product of Comparative Example 6. The shear viscosity is greatly improved. It is known that the addition of SPG monomer can greatly improve the zero shear viscosity of the polyester after solid state polymerization to achieve good processability.

Example 7

The same procedure as in Example 6 was carried out, wherein 1,3-propanediol was changed to 1,4-butanediol, and the temperature of the polycondensation reaction was 240 °C. The properties of the product are listed in Table 5.

As can be seen from the fifth table, the polyol monomer was changed to butanediol, and the solid polymerized polyester had a good zero shear viscosity.

Comparative Example 7

Similar to the method described in Example 2, the difference is that after the dimethyl 2,5-furandicarboxylate and the ethylene glycol are melt-polymerized, the SPG monomer is added together by melt-kneading to carry out solid state polymerization, and the solid state is solid. The polymerization time was changed to 24 hours. The intrinsic viscosity before the addition of the SPG monomer was 0.394 dL/g, and the intrinsic viscosity after the addition of the SPG monomer was 0.538 dL/g. The properties of the polyester product are listed in Table 6.

Example 8

1 part of dimethyl 2,5-furandicarboxylate, 2.5 moles of ethylene glycol, 1000 ppm (relative to the weight of dimethyl 2,5-furandicarboxylate, about 0.06046 mol%) , 9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane (hereinafter referred to as SPG monomer), relative to 100 ppm (relative to A titanium-based solid catalyst (manufactured by Dingxing Industrial Co., Ltd., C-94) in the weight of dimethyl 2,5-furandicarboxylate was placed in a reaction vessel and equipped with a condensing device and a methanol collecting cylinder. Nitrogen gas was introduced, and the salt bath temperature was set to 190 ° C, and the stirrer rotation speed was 200 rpm to carry out the transesterification reaction. When the catalyst is completely dissolved, methanol is condensed in the condenser, and the reaction is continued for 5 hours, after removing the condensed methanol and adding 0.1 wt% (relative to the weight of dimethyl 2,5-furandicarboxylate) of the antioxidant ( From Irganox 1010) from BASF, the pressure in the reaction system was gradually reduced to 50 torr in 30 minutes to remove excess ethylene glycol. The salt bath temperature was gradually increased to 230 ° C and the reaction pressure was gradually lowered to below 1 torr, and the reaction was continued for 60 minutes to carry out a polycondensation reaction. Finally, the vacuum was broken with nitrogen and the heating and stirring were stopped, the reaction tank lid was taken apart, and the viscous product was taken out.

The above product was recrystallized at a temperature of 150 ° C for 90 minutes, pulverized by a pulverizer and separated by a sieve, and a powder of less than 25 mesh was taken for solid state polymerization. The powder is placed in a reaction tank, the salt bath temperature is set to 200 ° C for solid-polymerization reaction, the reaction pressure is lower than 1 torr, and after 24 hours of reaction, a branched polyester is obtained, and the branched polyester is taken out to analyze the intrinsic viscosity. 0.51 dL/g.

The polyester was melted by heating to 260 ° C, and melt-spun by a 24-hole spinneret, and the discharge amount was 13.4 g/min. 20% PET oil in the spinning process Medium oil, and the oil amount is 0.316cc/min. The above spinning process was carried out under nitrogen. The cooled and solidified fibers were then taken up at a rate of 600 meters per minute to obtain a fiber bundle of 201 denier per 24 filaments, and the fiber properties were tested. The fibers were then further extended at 100 ° C and the properties of the fibers after extension were analyzed as shown in Table 7. The linear density measurement method is to measure the discharge volume and the winding rate by converting the weight of the 9000 m fiber to obtain a linear density. The measurement of fiber strength and elongation at break was carried out by a tensile tester USTER URT4 instrument. The melting point and crystallinity of the fibers were analyzed by a thermal differential scanning calorimeter (DSC) Q20 of TA Corporation and analyzed at a heating rate of 10 ° C/min under nitrogen.

Example 9

The method of forming the polyester was similar to that of Example 8, except that the solidification time was 30 hours, and the inherent viscosity of the polyester was about 0.55 dL/g. The polyester was melted by heating to 260 ° C, and melt-spun by a 24-hole spinneret, and the discharge amount was 13.4 g/min. 20% of the PET oil was oiled during the spinning process, and the oil amount was 0.316 cc/min. The above spinning process was carried out under nitrogen. The cooled and solidified fibers were then taken up at a rate of 600 meters per minute to obtain a fiber bundle of 201 denier per 24 filaments, and the fiber properties were tested. The fibers were then further extended at 100 ° C and the properties of the fibers after extension were analyzed as shown in Table 7.

Example 10

The method of forming the polyester was similar to that of Example 8, except that the solid solution time was 36 hours, so the inherent viscosity of the polyester was 0.60 dL/g. The polyester was melted by heating to 260 ° C, and melt-spun by a 24-hole spinneret, and the discharge amount was 13.7 g/min. 20% of the PET oil was oiled during the spinning process, and the oil amount was 0.316 cc/min. The above spinning process was carried out under nitrogen. Then take the cooling solid at a rate of 600 meters per minute. The resulting fibers were obtained with a fiber bundle of 206 denier/24 filaments and tested for fiber properties. The fibers were then further extended at 100 ° C and the properties of the fibers after extension were analyzed as shown in Table 7.

Example 11

The method of forming the polyester was similar to that of Example 8, except that the solid solution time was 36 hours, so the inherent viscosity of the polyester was 0.61 dL/g. The polyester was melted by heating to 270 ° C, and melt-spun by a 24-hole spinneret, and the discharge amount was 14 g/min. 20% of the PET oil was oiled during the spinning process, and the oil amount was 0.316 cc/min. The above spinning process was carried out under nitrogen. The cooled and solidified fibers were then taken up at a rate of 400 meters per minute to obtain a fiber bundle of 316 denier/24 filaments, and the fiber properties were tested. The fibers were then further extended at 100 ° C and the properties of the fibers after extension were analyzed as shown in Table 7.

Comparative Example 8

The method of forming the polyester was similar to that of Example 8, except that the SPG monomer was not contained in the reactant, and the inherent viscosity of the polyester was 0.58 dL/g. The polyester was melted by heating to 260 ° C, and melt-spun by a 24-hole spinneret, and the discharge amount was 13.5 g/min. 20% of the PET oil was oiled during the spinning process, and the oil amount was 0.316 cc/min. The above spinning process was carried out under nitrogen. The cooled solidified fibers were then taken up at a rate of 600 meters per minute and tested for fiber properties. The fibers were then further extended at 100 ° C and the properties of the fibers after extension were analyzed as shown in Table 7.

As can be seen from the seventh table, in comparison with the comparative example 8 in which the SPG monomer was added, the fiber strength was remarkably improved before and after the elongation, and the elongation at break was greatly improved. In addition, after the fiber of the embodiment is stretched, the crystallinity of the material is greatly improved, indicating that the SPG monomer is favorable for the formation of the branched structure of the polyester, thereby restricting the activity of the molecular chain of the polyester, and after extending the fiber, A crystallization mechanism that produces heterogeneous nucleation that promotes the rate of crystallization of the fiber during elongation. As the solidification reaction time prolongs, the molecular weight (intrinsic viscosity) gradually increases, and the degree of branching is gradually increased, and the effect of improving the strength of the PEF fiber is more obvious.

By DSC analysis of the thermal properties of the fiber after extension, it was found that the fiber of the example in which the SPG monomer was added had two distinct melting peaks, indicating that the branched structure produced by the modification of the SPG monomer produced two during the fiber extension process. A different crystalline phase in which the higher melting point may be caused by a heterogeneously crystallized polyester molecular chain.

The initial fiber winding rate also has a significant effect on fiber strength. Example 10 and Example 11 collected fibers at a winding rate of 600 and 400 m/min, respectively, and it was apparent that a higher spinning take-up rate corresponds to a higher fiber strength. Fibers that are wound at lower speeds do not reach the same fiber strength even after stretching. Therefore, the fiber strength of the SPG monomer modification can be further improved by increasing the winding rate.

Example 12

The method of forming the polyester was similar to that of Example 8, except that the ethylene glycol was changed to butanediol, and the inherent viscosity of the polyester was 0.716 dL/g. The polyester was melted by heating to 245 ° C, and melt-spun by a 24-hole spinneret, and the discharge amount was 11.8 g/min. 20% of the PET oil was oiled during the spinning process, and the oil amount was 0.316 cc/min. The above spinning process was carried out under nitrogen. The cooled and solidified fibers were then taken up at a rate of 600 meters per minute to obtain a fiber bundle of 177 denier per 24 filaments, and the fiber properties were tested. The fibers were then further extended at 100 ° C and the properties of the fibers after extension were analyzed as shown in Table 8.

Comparative Example 9

The method of forming the polyester was similar to that of Example 12 except that the reactant contained no SPG monomer and the inherent viscosity of the polyester was 0.784 dL/g. The polyester was melted by heating to 245 ° C, and melt-spun by a 24-hole spinneret, and the discharge amount was 11.8 g/min. 20% of the PET oil was oiled during the spinning process, and the oil amount was 0.316 cc/min. The above spinning process was carried out under nitrogen. The cooled and solidified fibers were then taken up at a rate of 600 meters per minute to obtain a fiber bundle of 177 denier per 24 filaments, and the fiber properties were tested. The fibers were then further extended at 100 ° C and the properties of the fibers after extension were analyzed as shown in Table 8.

It can be seen from the eighth table that the fiber having a branched structure has a higher fiber strength at a lower viscosity characteristic under the condition that the fiber has a stretching ratio of 3 times. Degree and elongation of elongation. The SPG monomer is used as a branched structural modification monomer, and the application to the fiber material also enhances the mechanical properties of the fiber. Fibers having a branched structure have a higher back extension ratio and can reach 3.4 times. Although the fiber modified without SPG monomer has higher viscosity characteristics, the subsequent stretching ratio can only reach 3.2 times.

Example 13

The formation of the polyester was similar to that of Example 8, except that the ethylene glycol was changed to propylene glycol, the solid polymerization time was 24 hours, and the inherent viscosity of the polyester was 0.883 dL/g. The polyester was melted by heating to 245 ° C, and melt-spun by a 24-hole spinneret, and the discharge amount was 13.2 g/min. 20% of the PET oil was oiled during the spinning process, and the oil amount was 0.316 cc/min. The above spinning process was carried out under nitrogen. The cooled and solidified fibers were then taken up at a rate of 500 meters per minute to obtain a fiber bundle of 237 denier per 24 filaments, and the fiber properties were tested. After the fiber was left at room temperature for a period of time, it was shrunk to form a fiber bundle of 320 denier/24 filaments. The fibers were then further extended at 110 ° C (extension rate of 3 m/min) and the properties of the fibers after extension were analyzed as shown in Table 9.

Example 14

The formation of the polyester was similar to that of Example 13, except that the solidification time was 36 hours, so the inherent viscosity of the polyester was 1.2 dL/g. The polyester was melted by heating to 255 ° C, and melt-spun by a 24-hole spinneret, and the discharge amount was 13.2 g/min. 20% of the PET oil was oiled during the spinning process, and the oil amount was 0.316 cc/min. The above spinning process was carried out under nitrogen. The cooled and solidified fibers were then taken up at a rate of 600 meters per minute to obtain a fiber bundle of 191 denier per 24 filaments, and the fiber properties were tested. After the fiber was left at room temperature for a period of time, it shrank to form a fiber bundle of 427 denier/24 filaments. The fibers were then further extended at 110 ° C (extension rate of 3 m/min) and the properties of the fibers after extension were analyzed as shown in Table 9.

Comparative Example 10

The method of forming the polyester was similar to that of Example 13, except that the SPG monomer was not contained in the reaction product, and the solid polymerization reaction was not carried out, and the inherent viscosity of the polyester was 0.774 dL/g. The polyester was melted by heating to 245 ° C, and melt-spun by a 24-hole spinneret, and the discharge amount was 13.9 g/min. 20% of the PET oil was oiled during the spinning process, and the oil amount was 0.316 cc/min. The above spinning process was carried out under nitrogen. The cooled and cured fiber bundles were then taken up at a rate of 600 meters per minute and tested for fiber properties. The fiber was then further extended at 110 ° C (extension rate of 3 m/min), and the fiber was broken as soon as it extended, i.e., the fiber could not be stretched.

As can be seen from the table 9, the fiber material obtained by the polyester at a winding rate of less than 600 m/min has a relatively low fiber strength and elongation at break. Although the polyester with branched structure has higher viscosity characteristics, the lower winding rate still has no better fiber strength performance. Example 13 had a lower winding speed (500 m/min) and a lower fiber strength than the polyester fiber of Comparative Example 10 which was not modified and had lower viscosity characteristics. This result is consistent with the results of the low-winding-spun polyester fibers of the foregoing examples having lower fiber strength. In addition, the post extension method can increase the fiber strength. The polyester fiber which was not modified by SPG in Comparative Example 10 was not extensible, and the fiber strength could not be increased in a later manner. Examples 13 and 14 have a branched structure of a polyester material. Fiber elongation was carried out at a low elongation rate (3 m/min). When the stretching ratio is higher, the fiber strength is also increased, and the elongation at break is also significantly increased after the extension. In summary, the branched structure produced by SPG can enhance the characteristics of polyester fibers.

It can be seen from the above examples and comparative examples that the branched structure formed by adding the SPG monomer can greatly improve the strength and elongation of the fiber, and overcome the low entanglement density of the polyester material, thereby improving the mechanical properties of the fiber. In addition, the addition of SPG monomer can shorten the reaction time required for solid-state polymerization in the preparation of polyester, and can also reduce the hue change caused by long-time high-temperature polymerization.

The present disclosure has been disclosed in the above several embodiments, but it is not intended to limit the disclosure, and any one skilled in the art can make any changes and refinements without departing from the spirit and scope of the disclosure. Therefore, the scope of protection of this disclosure is subject to the definition of the scope of the patent application.

Claims (14)

A fiber comprising: a polyester obtained by copolymerizing a diacid, a diacid ester, or a combination thereof with a polyol, wherein the diacid, the ester of the diacid, or a combination thereof comprises (1) a furan dicarboxylic acid, a furan dicarboxylate, or a combination thereof, or (2) a furan dicarboxylic acid, a furan dicarboxylate, or a combination thereof and a spirobiic acid, and the polyol comprises (3) C _{a 2-} C ₁₄ polyol or (4) a C ₂ -C ₁₄ polyol and a spiro diol, wherein the spiro diol has the structure of formula (I): Wherein the spirobiic acid has the structure of formula (II): Wherein each R ^{2 is} independently a single bond, , , Or a linear alkylene group of C ₁ -C ₄ , each R ^{3 is} independently or And the diacid, the ester of the diacid, or a combination thereof, is compatible with the polyol: (a) the diacid, the ester of the diacid, or a combination thereof comprising (2) the furan dicarboxylic acid, The furandicarboxylate, or a combination thereof, and the spirobiic acid, (b) the polyol comprises (4) the C ₂ -C ₁₄ polyol and the spiro diol, or (c) a combination wherein the polyester has an intrinsic viscosity at 30 ° C of between 0.5 dL/g and 1.5 dL/g, and when the diacid, the ester of the diacid, or a combination thereof comprises 1 mole ( 1) the furan dicarboxylic acid, the furan dicarboxylate, or a combination thereof, and the polyol comprises 1 to 3 moles of (4) the C ₂ -C ₁₄ polyol and the spirodiol Wherein the furan dicarboxylic acid, the furan dimethyl ester, or a combination of the above and the spirocyclic diol is 1:0.0003023 to 1:0.0012092; when the diacid, the ester of the diacid, Or a combination of the above comprising 1 part of (2) the furan dicarboxylic acid, the furan dicarboxylate, or a combination thereof and the spirobiic acid, the polyol comprising 1 to 3 moles (3) ) the C ₂ -C A polyol of ₁₄ , wherein the furan dicarboxylic acid, the furan dicarboxylate, or a combination of the above and the spirobiic acid molar ratio is 99.998: 0.002 to 99.9999: 0.0001. The fiber of claim 1, wherein the fiber has an elongation at break of between 5% and 200%. The fiber according to claim 1, wherein the fiber has a crystallinity of between 5 J/g and 60 J/g. The fiber of claim 1, wherein the furan dicarboxylic acid comprises 2,5-furandicarboxylic acid, 3,4-furandicarboxylic acid, 2,3-furandicarboxylic acid or a combination thereof. The fiber according to claim 1, wherein the furan dimethyl ester comprises dimethyl 2,5-furandicarboxylate, dimethyl 3,4-furandicarboxylate, and 2,3-furodicarboxylic acid. Dimethyl or a combination of the above. The fiber according to claim 1, wherein the C ₂ -C ₁₄ polyol comprises ethylene glycol, 1,3-propanediol, glycerol, 1,4-butanediol, 1,5-pentane Glycol, neopentyl glycol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, decanediol, undecanediol, Dodecanediol, tetradecanediol, rosindiol, isosorbide, 2,5-furandiol, or a combination thereof. A method for producing a fiber comprising: mixing a diacid, a diacid ester, or a combination thereof; and a polyol to carry out an esterification reaction and a polycondensation reaction to form a prepolymer; and solid-polymerizing the prepolymer, Forming a polyester; and spinning the polyester to form a fiber, wherein the diacid, the ester of the diacid, or a combination thereof comprises (1) furan dicarboxylic acid, furan diformate, or a combination of the above or (2) furan dicarboxylic acid, a furan dicarboxylate, or a combination thereof, and a spirobiic acid, and the polyol comprises (3) a C ₂ -C ₁₄ polyol or (4) C ₂ -C ₁₄ polyol and spiro diol, wherein the spiro diol has the structure of formula I: Wherein the spirobiic acid has the structure of formula II: Wherein each R ^{2 is} independently a single bond, , , Or a linear alkylene group of C ₁ -C ₄ , each R ^{3 is} independently , or And the diacid, the ester of the diacid, or a combination thereof, is compatible with the polyol: (a) the diacid, the ester of the diacid, or a combination thereof comprising (2) the furan dicarboxylic acid, The furandicarboxylate, or a combination thereof, and the spirobiic acid, (b) the polyol comprises (4) the C ₂ -C ₁₄ polyol and the spiro diol, or (c) a combination wherein the polyester has an intrinsic viscosity at 30 ° C of between 0.5 dL/g and 1.5 dL/g, and when the diacid, the ester of the diacid, or a combination thereof comprises 1 mole (1) the furan dicarboxylic acid, the furan dimethyl ester, or a combination thereof, and the polyol comprises 1 to 3 moles of (4) the C ₂ -C ₁₄ polyol and the spiro 2 An alcohol, wherein the furan dicarboxylic acid, the furan dimethyl ester, or a combination of the above and the spirocyclic diol is 1:0.0003023 to 1:0.0012092; when the diacid, the acid ester of the diacid Or a combination of the above comprising 1 mole of (2) the furan dicarboxylic acid, the furan dicarboxylate, or a combination thereof and the spirobiic acid, the polyol comprising 1 to 3 moles ( 3) The C ₂ a polyhydric alcohol of -C ₁₄ wherein the furan dicarboxylic acid, the furan dicarboxylate, or a combination thereof and the spirobiic acid molar ratio 99.998: 0.002 to 99.9999: 0.0001. The method for producing a fiber according to claim 7, further comprising collecting the fiber at a winding rate between 100 m/min and 3000 m/min. The method for producing a fiber according to claim 7, further comprising extending the fiber at a temperature of from 60 ° C to 150 ° C, and the length of the fiber after the extension is between 1.1 and 5 times the length of the fiber before the stretching. The method for producing a fiber according to claim 7, wherein the fiber has an elongation at break of between 5% and 200%. The method for producing a fiber according to claim 7, wherein the fiber has a crystallinity of from 5 J/g to 60 J/g. The method for producing a fiber according to claim 7, wherein the furan dicarboxylic acid comprises 2,5-furandicarboxylic acid, 3,4-furandicarboxylic acid, 2,3-furandicarboxylic acid or a combination thereof. The method for producing a fiber according to claim 7, wherein the furan dimethyl ester comprises dimethyl 2,5-furandicarboxylate, dimethyl 3,4-furandicarboxylate, 2,3- Dimethyl furan dicarboxylate or a combination thereof. The method for producing a fiber according to claim 7, wherein the C ₂ -C ₁₄ polyol comprises ethylene glycol, 1,3-propanediol, glycerin, 1,4-butanediol, 1, 5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, decanediol, undecane A diol, dodecanediol, tetradecanediol, rosin diol, isosorbide, 2,5-furan diol or a combination thereof.